CN106082159A - The preparation method of Folium Pini shape CNT/network combined material with carbon element of electric conduction of carbon fiber - Google Patents
The preparation method of Folium Pini shape CNT/network combined material with carbon element of electric conduction of carbon fiber Download PDFInfo
- Publication number
- CN106082159A CN106082159A CN201610388144.8A CN201610388144A CN106082159A CN 106082159 A CN106082159 A CN 106082159A CN 201610388144 A CN201610388144 A CN 201610388144A CN 106082159 A CN106082159 A CN 106082159A
- Authority
- CN
- China
- Prior art keywords
- carbon
- cnt
- preparation
- carbon fiber
- fibre fabric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Fibers (AREA)
- Catalysts (AREA)
Abstract
The preparation method of a kind of Folium Pini shape CNT/network combined material with carbon element of electric conduction of carbon fiber, described preparation method is with the fiber of carbon fibre fabric as growth substrate, the CNT of growing high density arrangement in described growth substrate；The CNT of institute's growing high density arrangement forms three-dimensional porous Folium Pini shape CNT/network combined material with carbon element of electric conduction of carbon fiber together with carbon fiber substrates, having high specific surface area is to support the ideal material of active substance or reacting substance, excellent mechanical strength can suppress material structural deterioration in course of reaction, CNT and carbon fiber intersect or the integrity of overlying contact beneficially raising composite material conductive framework simultaneously, this composite is at fuel cell, ultracapacitor, lithium sky battery, lithium-sulfur cell and organic solar batteries etc. are with a wide range of applications.
Description
Technical field
The present invention relates to the preparation method of a kind of CNT/carbon fiber complex carbon material, specifically a kind of at carbon fiber
In the carbon fiber substrates that fabric overlap is staggered, chemical vapour deposition technique is utilized to prepare the Folium Pini shape carbon nanometer of high-density array
The network combined material with carbon element of pipe/electric conduction of carbon fiber.
Background technology
CNT is the important a member in " Nanometer World ", is constantly in the Disciplinary Frontiers of international scientific in recent years.Carbon
Nanotube can regard as by graphene sheet layer curling form, can be divided into according to the number of plies of graphene film: SWCN and
Multi-walled carbon nano-tubes.In general, SWCN is more complete and have higher chemical inertness due to its surface texture, with
The increase of tube wall layer number, produce more defect in its surface so that physical and chemical activity strengthens.Multi-walled carbon nano-tubes has
The characteristics such as specific surface area is big, mechanical strength is high, surface activity is the most active are had to be paid close attention to by numerous researchers and study.
In view of multi-walled carbon nano-tubes has the structure of uniqueness and excellent conductive characteristic, at nanoelectronic equipment, carrier material
The aspects such as material and hydrogen storage material are respectively provided with potential using value, and therefore the preparation of multi-walled carbon nano-tubes is carried out by researchers
Substantial amounts of research work, mainly has arc discharge method, laser evaporization method, chemical vapour deposition technique etc..Since 1991, many walls carbon
Nanotube first arc discharge method [Curl R.F. and Smalley R.E. Fullerenes [J]. Scientific
American, 1991, (10): 54-63.] produce the cathode deposit of fullerene find since, about CNT
Preparation in constantly exploring and improving, achieve major progress.In recent years, chemical vapour deposition technique is used to prepare on a large scale
Multi-walled carbon nano-tubes develops into a kind of more ripe method, and its principle is to be urged by carbonaceous gas or fluid organic material
Crack under agent effect, deposit thus grow CNT.The caliber of the CNT prepared and pipe range can effectively control, pipe
Wall is relatively clean and surface activity is higher.At [Li Wenzhi, et al. Chemical Physics such as calendar year 2001 Li
Letter, 2001,335 (3-4): 141 149.] utilize chemical vapor infiltration to give birth to directly on a surface at pure graphite granule
Long CNT, has prepared CNT/graphite composite material.This material because fully utilizing the advantage of conductive substrates,
Thus improve its application in electrochemistry equipment to a certain extent.But, this CNT/graphite composite material is big
Mostly being the powder shaped CNT piling up the lack of alignment formed, they do not have three-dimensional porous structure, and conductive frame is imperfect,
The most limited.Subsequently, [Li Y, Huang Z, Huang K, the et al. Hybrid Li-air such as Li
battery cathodes with sparse carbon nanotube arrays directly grown on carbon
Fiber papers [J]. Energy Environmental Science, 2013,6 (11): 3339-3345.]
Use electrodeposition process carrying inorganic metallic catalyst on the carbon fiber of carbon paper, utilize chemical vapour deposition technique in the side of carbon fiber
It is successfully prepared sparse array type CNT.Although the CNT at grown on carbon fibers has certain array type knot
Structure, but first quotation is catalyst load process method is complex, and control condition harshness is difficult to carry out.Secondly, the party
Method is only at the carbon nano pipe array that the growth of the side of carbon fiber is sparse, and the opposite side of carbon fiber does not the most grow carbon nanometer
Pipe, thus it is less to result in carbon nano tube growth amount.Therefore, improving the utilization rate of carbon fiber-based basal surface, growing high density is arranged
The CNT of row, thus the integrity improving conductive frame further becomes the practical problem that must solve.
Summary of the invention
It is an object of the invention to utilize chemical vapour deposition technique to prepare high density on the carbon fiber of carbon fibre fabric
The Folium Pini shape CNT/network combined material with carbon element of electric conduction of carbon fiber of arrangement, and a kind of Folium Pini shape CNT/carbon fiber is provided
The preparation method of conductive network complex carbon material.
The technical solution used in the present invention is as follows:
The preparation method of a kind of Folium Pini shape CNT/network combined material with carbon element of electric conduction of carbon fiber, described preparation method is with carbon
The fiber of fabric is growth substrate, the CNT of growing high density arrangement in described growth substrate；Wherein, described fibre
Dimension diameter is 3-10 μm, and the length of described CNT is 5-150 μm, and the diameter of described CNT is 20-220nm, described
The arranging density of CNT is 1 × 1021-220×1021Root/m2。
The concrete preparation method of technique scheme follows these steps to carry out:
(1) the fiber surface pretreatment of carbon fibre fabric
Carbon fibre fabric is placed in ultrasonic cleaning 10-60min in isopropanol or ethanol solution, and dries at a temperature of 60-100 DEG C
Dry 20-60min；After will clean after fabric be placed in tube furnace, control temperature between 500-700 DEG C, at argon atmosphere
Lower calcining 1-12h, carries out high temperature unsticking process to fiber surface；
Carbon fibre fabric high-temperature process crossed is immersed in has in the solution of strong oxidizing property 1-6 hour, takes out and at 60-100
Dry 1-8h at a temperature of DEG C, obtain the carbon fibre fabric of surface cleaning；Inorganic metal catalysis is weighed the most in mass ratio for 25-35:1
Agent presoma and carbohydrate polymer, be dissolved in Ludox and the mixed solvent of surfactant composition that volume ratio is 5-10:1
In, magnetic agitation 6-36h under room temperature, configuration obtains inorganic metal catalyst precursor solution；After by the carbon of above-mentioned surface cleaning
Fabric carries out sucking filtration, 50-100 DEG C of temperature after being placed in inorganic metal catalyst precursor solution immersion 10-120min
Lower drying 3-24h, repeats 1-10 time, makes the carbon fiber surface on fabric wrap up one layer of inorganic metal catalyst presoma equably
With carbohydrate polymer mixture, obtain the carbon fibre fabric of pretreatment；
(2) carbon source is prepared with organo-metallic catalyst precursor mixed solution
Using the material containing aromatic rings class as carbon source, with containing in iron-based, cobalt-based and Ni-based organo-metallic compound
Planting or several as organo-metallic catalyst presoma, organic metal ion concentration in carbon source is 0.01-0.3g/ml；Will
This solution ultrasonic disperse 10-90min, prepares the mixed solution of carbon source and organo-metallic catalyst presoma；
(3) prepared by Folium Pini shape CNT/network combined material with carbon element of electric conduction of carbon fiber
The carbon fibre fabric of step (1) pretreatment is placed in tube furnace warm area with the angle of 0-180 DEG C, uses chemical gaseous phase to sink
Area method, using argon, nitrogen, helium one or more mix as carrier gas for 1-10:1 by volume with hydrogen, tube furnace with
The ramp of 1-10 DEG C/min is to 600-900 DEG C；Mixed solution step (2) configured is with the linear speed of 0.4-2.0ml/min
Degree is injected in tube furnace, keeps reaction furnace pressure constant, and growth time is 15-120min, and growth closes carrier gas after terminating,
When temperature reaches 400-700 DEG C under air atmosphere purifying carbon nano-tube, treat that room temperature is down to by tube furnace, obtain at carbon fibre fabric
The Folium Pini shape CNT of upper preparation/network combined material with carbon element of electric conduction of carbon fiber.
Further, additional technical feature is as follows.
Described carbon fibre fabric is carbon cloth, carbon fiber tape, carbon fiber paper, carbon fiber felt, carbon fiber seat and carbon fiber
One in sheet material.
Described strong oxidizing property solvent is the one in concentrated nitric acid, concentrated sulphuric acid and hydrogen peroxide, and wherein concentrated nitric acid and concentrated sulphuric acid are
It is allowed to a kind of or mixing of arbitrary proportion.
Described inorganic metal compound be ferric nitrate, iron chloride, iron phosphate, iron sulfate, iron sulfide, cobalt nitrate, cobaltous chloride,
One in C.I. Pigment Violet 14, cobaltous sulfate, cobalt sulfide, nickel nitrate, Nickel dichloride., nickel phosphate, nickel sulfate and nickel sulfide or arbitrarily mix.
Described Ludox is the one in neutral Ludox, acidic silicasol and alkaline silica sol, wherein solid titanium dioxide
Silicone content is 20%-40%.
Described carbohydrate polymer is in glucose, fructose, starch, sucrose, glycogen, maltodextrin and cellulose acetate
A kind of or arbitrarily mix.
Described surfactant be ethanol, normal propyl alcohol, isopropanol, sodium lauryl sulphate, oleic acid, dodecyl sodium sulfate,
Dodecylbenzene sodium sulfonate, cetab, lecithin, fatty glyceride, polyvinyl pyrrolidone, washing
One in agent and organic amine soap.
The material of described aromatic rings class is benzene,toluene,xylene, styrene, benzyl alcohol, benzaldehyde, methyl phenyl ethers anisole, benzene first
One in amine, benzonitrile, phenylacetic acid, polypyrrole, polythiophene, polyaniline, nitroaniline, Bispyrithione and 2-methylimidazole
Or arbitrarily mix.
Described metallo-organic compound is ferrocene, carbonyl iron, ferric oxalate, iron acetate, ethylenediamine conjunction ferrum, cobaltocene, carbonyl
One in base cobalt, cobalt oxalate, cobaltous acetate, triethylenediamine cobalt, dicyclopentadienyl nickel, Nickel tetracarbonyl., nickel oxalate, nickel acetate and ethylenediamine nickel
Or arbitrarily mix.
The preparation side of above-mentioned provided a kind of Folium Pini shape CNT/network combined material with carbon element of electric conduction of carbon fiber is provided
Method, in the carbon fiber substrates that carbon fibre fabric overlap is staggered, utilizes chemical vapour deposition technique to be prepared for a kind of Folium Pini shape carbon and receives
The network combined material with carbon element of mitron/electric conduction of carbon fiber.Especially with the carbon fiber on carbon fibre fabric as carrier, add carbon
Fiber surface and the contact area of catalyst, solve the problem that carbon fiber substrates surface utilisation is low, structure between CNT
The problem of poor stability, the incomplete problem of conductive frame, and low the asking of CNT stand density in conductive substrates
Topic, it is achieved that the conductive network structure that the CNT of a kind of high-density array is integrated with substrate.
CNT/carbon fibre composite prepared by this method has carbon fiber and receives with carbon with carbon fiber, CNT
Mitron, carbon fiber are interlaced with CNT contacts the three-dimensional porous conductive network structure of formation, not only makes material have higher
Specific surface area, complete conductive frame；And more active substance or reacting substance can be loaded, preparation process makes
With the carbon fiber of carbohydrate polymer cladding, can be effectively improved material increases the stability of material structure.
The Folium Pini shape CNT that the present invention is prepared by chemical vapour deposition technique/electric conduction of carbon fiber network combined carbon material
Material, will have at fuel cell, ultracapacitor, lithium sky battery, lithium-sulfur cell and organic solar batteries etc. and widely should
Use prospect.For lithium-sulfur cell, Folium Pini shape CNT/network combined material with carbon element of electric conduction of carbon fiber can provide the most direct with
Unobstructed electronic conduction path, the anode structure carrying sulfur content and high mechanical properties big in carbon nano tube surface is to improving lithium sulfur electricity
Pond chemical property has positive meaning.Additionally, this preparation method can effectively control the stand density of CNT, caliber and pipe
Long etc., further increase the actual application value of this material.
Accompanying drawing explanation
Fig. 1 is the structural representation of carbon paper internal carbon fibers.
Fig. 2 is the structural representation preparing Folium Pini shape CNT/carbon fibre composite in individual carbon fibers.
Fig. 3 is this method undressed carbon paper carbon fiber SEM figure.
Fig. 4 is that this method is schemed through the carbon paper carbon fiber SEM of Overheating Treatment.
Fig. 5 is that this method is schemed through the carbon paper carbon fiber SEM of peracid treatment.
Fig. 6 is the carbon paper carbon fiber SEM figure after this method soaks inorganic metal catalyst precursor solution.
Fig. 7 is that the present invention prepares under certain growth conditions and has array type CNT/carbon fibre composite
SEM schemes.
Fig. 8 is the SEM that the present invention prepares Folium Pini shape CNT/carbon fibre composite under optimal growth conditions
Figure.
Detailed description of the invention
Below the detailed description of the invention of the present invention is further illustrated.
Embodiment 1
(1) pretreatment of carbon fibre fabric
First, carbon fibre fabric carries out ultrasonic cleaning 20min in isopropanol, dries 20min at a temperature of 80 DEG C；Secondly, right
The sizing agent of carbon fiber surface thermally decomposes, and calcines 6h in tube furnace, and temperature is 600 DEG C；Then, to carbon fibre fabric table
Face carries out acid treatment, soaks 3h in concentrated nitric acid, dries 4h, obtain the carbon fibre fabric of surface cleaning at a temperature of 60 DEG C；Connect
, weigh 6.06g ferric nitrate and 0.2g sucrose is dissolved in the solvent of 15g Ludox and 2ml ethanol, magnetic agitation under room temperature
12h, configuration obtains inorganic metal catalyst precursor solution；Finally, the carbon fibre fabric of surface cleaning is immersed in inorganic gold
60min in metal catalyst precursor solution, dries 5h at 80 DEG C after sucking filtration 2min.This process is repeated 2 times, and makes ferric nitrate and sugarcane
Sugar is uniformly adhered on carbon fiber, obtains the carbon fibre fabric of pretreatment.
(2) configuration carbon source and the mixed solution of organo-metallic catalyst presoma
With dimethylbenzene as carbon source, with ferrocene for organo-metallic catalyst presoma, concentration is 0.05g/ml, is carried out by this solution
Ultrasonic 40min, obtains the mixed solution of carbon source and organo-metallic catalyst presoma.
(3) preparation of Folium Pini shape CNT/carbon fibre composite
The carbon fibre fabric of step (1) pretreatment is placed in tube furnace warm area with 90 °, uses chemical vapour deposition technique, argon
The gaseous mixture of 900ml/min and hydrogen 210ml/min is carrier gas, tube furnace with the ramp of 5 DEG C/min to 700 DEG C；Will step
Suddenly the mixed solution that (2) configure is expelled in tube furnace with the linear velocity of 0.8ml/min, and keeps reaction furnace pressure constant,
The time of growth CNT is 60min, and growth closes carrier gas after terminating, when temperature reaches 450 DEG C under air atmosphere purification
CNT, treats that tube furnace is down to room temperature and is obtained the Folium Pini shape CNT/carbon fiber composite of preparation on carbon fibre fabric
Material.
Embodiment 2
(1) pretreatment of carbon fibre fabric
First, carbon fibre fabric carries out ultrasonic cleaning 40min in ethanol solution, dries 20min at a temperature of 60 DEG C；Secondly,
Thermally decomposing the sizing agent of carbon fiber surface, calcine 7h in Muffle furnace, temperature is 400 DEG C；Then, to carbon fibre fabric
Surface carries out acid treatment, soaks 6h in concentrated sulphuric acid, dries 4h, obtain the carbon fibre fabric of surface cleaning at a temperature of 60 DEG C；Connect
, weigh 8.08g cobalt nitrate and 0.27g glucose is dissolved in the solvent of 20g Ludox and 4ml b propanol, magnetic force under room temperature
Stirring 12h, configuration obtains inorganic metal catalyst precursor solution；Finally, the carbon fibre fabric of surface cleaning is immersed in nothing
60min in organic metal catalyst precursor solution, dries 5h at 80 DEG C after sucking filtration 2min.This process is repeated 4 times, and makes cobalt nitrate
It is uniformly adhered on carbon fiber be uniformly adhered on carbon fiber with glucose, obtains the carbon fibre fabric of pretreatment.
(2) configuration carbon source and the mixed solution of organo-metallic catalyst presoma
With toluene as carbon source, with cobaltocene for organo-metallic catalyst presoma, concentration is 0.30g/ml, is surpassed by this solution
Sound 40min, obtains the mixed solution of carbon source and organo-metallic catalyst presoma.
(3) preparation of Folium Pini shape CNT/carbon fibre composite
The carbon fibre fabric of step (1) pretreatment is placed in tube furnace warm area with 45 °, uses chemical vapour deposition technique, argon
The gaseous mixture of 800ml/min and hydrogen 160ml/min is carrier gas, tube furnace with the ramp of 5 DEG C/min to 600 DEG C；Will step
Suddenly the mixed solution that (2) configure is expelled in tube furnace with linear velocity for 1.0ml/min, and keeps reaction furnace pressure constant,
The time of growth CNT is 40min, and growth closes carrier gas after terminating, when temperature reaches 400 DEG C under air atmosphere purification
CNT, treats that tube furnace is down to room temperature and is obtained the Folium Pini shape CNT/carbon fiber composite of preparation on carbon fibre fabric
Material.
Embodiment 3
(1) pretreatment of carbon fibre fabric
First, carbon fibre fabric carries out ultrasonic cleaning 30min in ethanol solution, dries 20min at a temperature of 80 DEG C；Secondly,
Thermally decomposing the sizing agent of carbon fiber surface, calcine 6h in Muffle furnace, temperature is 400 DEG C；Then, to carbon fibre fabric
Surface carries out acid treatment, and in the solution that concentrated nitric acid and concentrated sulphuric acid volume ratio are 1:1, middle immersion 3h, dries at a temperature of 60 DEG C
4h, obtains the carbon fibre fabric of surface cleaning；Then, weigh 16.16g nickel nitrate and 0.27g maltodextrin is dissolved in 20g silicon
In the solvent of colloidal sol and 4ml b propanol, magnetic agitation 18h under room temperature, configuration obtains inorganic metal catalyst precursor solution；?
After, the carbon fibre fabric of surface cleaning is immersed in 30min in inorganic metal catalyst precursor solution, 80 after sucking filtration 2min
5h is dried at DEG C.This process is repeated 4 times, and makes nickel nitrate and Fructus Hordei Germinatus saccharin be uniformly adhered on carbon fiber, obtains pretreatment
Carbon fibre fabric.
(2) configuration carbon source and the mixed solution of organo-metallic catalyst presoma
With polythiophene as carbon source, with dicyclopentadienyl nickel for organo-metallic catalyst presoma, concentration is 0.08g/ml, is carried out by this solution
Ultrasonic 40min, obtains the mixed solution of carbon source and organo-metallic catalyst presoma.
(3) preparation of Folium Pini shape CNT/carbon fibre composite
The carbon fibre fabric of step (1) pretreatment is placed in tube furnace warm area with 30 °, uses chemical vapour deposition technique, argon
The gaseous mixture of 700ml/min and hydrogen 200ml/min is carrier gas, tube furnace with the ramp of 5 DEG C/min to 800 DEG C；Will step
Suddenly the mixed solution that (2) configure is expelled in tube furnace with linear velocity for 1.0ml/min, and keeps reaction furnace pressure constant,
The time of growth CNT is 48min, and growth closes carrier gas after terminating, when temperature reaches 600 DEG C under air atmosphere purification
CNT, treats that tube furnace is down to room temperature and is obtained the Folium Pini shape CNT/carbon fiber composite of preparation on carbon fibre fabric
Material.
Embodiment 4
(1) pretreatment of carbon fibre fabric
First, carbon fibre fabric carries out ultrasonic cleaning 30min in ethanol solution, dries 20min at a temperature of 80 DEG C；Secondly,
Thermally decomposing the sizing agent of carbon fiber surface, calcine 6h in Muffle furnace, temperature is 600 DEG C；Then, to carbon fibre fabric
Surface carries out acid treatment, and in hydrogen peroxide solution, middle immersion 3h, dries 4h at a temperature of 60 DEG C, obtain the carbon fiber of surface cleaning
Fabric；Then, weigh 8.08g Nickel dichloride. and 0.2g fructose is dissolved in the solvent of 25g Ludox and 6ml b propanol, under room temperature
Magnetic agitation 16h, configuration obtains inorganic metal catalyst precursor solution；Finally, the carbon fibre fabric of surface cleaning is soaked
60min in inorganic metal catalyst precursor solution, dries 5h at 80 DEG C after sucking filtration 2min.This process is repeated 6 times, and makes chlorine
Change nickel and fructose is uniformly adhered on carbon fiber, obtain the carbon fibre fabric of pretreatment.
(2) configuration carbon source and the mixed solution of organo-metallic catalyst presoma
With benzene as carbon source, with nickel acetate for organo-metallic catalyst presoma, concentration is 0.2g/ml, carries out ultrasonic by this solution
40min, obtains the mixed solution of carbon source and organo-metallic catalyst presoma.
(3) preparation of Folium Pini shape CNT/carbon fibre composite
The carbon fibre fabric of step (1) pretreatment is placed in tube furnace warm area with 0 °, uses chemical vapour deposition technique, argon
The gaseous mixture of 700ml/min and hydrogen 100ml/min is carrier gas, tube furnace with the ramp of 5 DEG C/min to 800 DEG C；Will step
Suddenly the mixed solution that (2) configure is expelled in tube furnace with linear velocity for 1.2ml/min, and keeps reaction furnace pressure constant,
The time of growth CNT is 30min, and growth closes carrier gas after terminating, when temperature reaches 660 DEG C under air atmosphere purification
CNT, treats that tube furnace is down to room temperature and is obtained the Folium Pini shape CNT/carbon fiber composite of preparation on carbon fibre fabric
Material.
Embodiment 5
(1) pretreatment of carbon fibre fabric
First, carbon fibre fabric carries out ultrasonic cleaning 20min in aqueous isopropanol, dries 20min at a temperature of 80 DEG C；Its
Secondary, the sizing agent of carbon fiber surface is thermally decomposed, in tube furnace, calcines 9h, temperature is 400 DEG C；Then, to carbon fiber
Fabric face carries out acid treatment, and in the mixed solution that nitric acid and sulphuric acid volume ratio are 2:1, middle immersion 3h, dries at a temperature of 60 DEG C
Dry 4h, obtains the carbon fibre fabric of surface cleaning；Then, weigh 10g iron chloride and 0.4g starch dissolution at 30g Ludox and
In the solvent of 8ml b propanol, magnetic agitation 12h under room temperature, configuration obtains inorganic metal catalyst precursor solution；Finally, will
The carbon fibre fabric of surface cleaning is immersed in 60min in inorganic metal catalyst precursor solution, after sucking filtration 2min at 80 DEG C
Dry 5h.This process is repeated 7 times, and makes iron chloride and starch be uniformly adhered on carbon fiber, and the carbon fiber obtaining pretreatment is knitted
Thing.
(2) configuration carbon source and the mixed solution of organo-metallic catalyst presoma
With polypyrrole as carbon source, with iron acetate for organo-metallic catalyst presoma, concentration is 0.15g/ml, is carried out by this solution
Ultrasonic 40min, obtains the mixed solution of carbon source and organo-metallic catalyst presoma.
(3) preparation of Folium Pini shape CNT/carbon fibre composite
The carbon fibre fabric of step (1) pretreatment is placed in tube furnace warm area with 60 °, uses chemical vapour deposition technique, argon
The gaseous mixture of 600ml/min and hydrogen 100ml/min is carrier gas, tube furnace with the ramp of 5 DEG C/min to 750 DEG C；Will step
Suddenly the mixed solution that (2) configure is expelled in tube furnace with linear velocity for 0.9ml/min, and keeps reaction furnace pressure constant,
The time of growth CNT is 50min, and growth closes carrier gas after terminating, when temperature reaches 550 DEG C under air atmosphere purification
CNT, treats that tube furnace is down to room temperature and is obtained the Folium Pini shape CNT/carbon fiber composite of preparation on carbon fibre fabric
Material.
Embodiment 6
(1) pretreatment of carbon fibre fabric
First, carbon fibre fabric carries out ultrasonic cleaning 30min in ethanol solution, dries 20min at a temperature of 80 DEG C；Secondly,
Thermally decomposing the sizing agent of carbon fiber surface, calcine 8h in tube furnace, temperature is 450 DEG C；Then, to carbon fibre fabric
Surface carries out acid treatment, and in the mixed solution that nitric acid and sulphuric acid volume ratio are 3:1, middle immersion 2h, dries at a temperature of 60 DEG C
4h, obtains the carbon fibre fabric of surface cleaning；Then, weigh 15g cobaltous chloride and 0.8g cellulose acetate is dissolved in 30g Ludox
With in the solvent of 6ml normal propyl alcohol, magnetic agitation 12h under room temperature, configuration obtains inorganic metal catalyst precursor solution；Finally,
The carbon fibre fabric of surface cleaning is immersed in 30min in inorganic metal catalyst precursor solution, at 80 DEG C after sucking filtration 2min
Lower drying 5h.This process is repeated 6 times, and makes cobaltous chloride and cellulose acetate be uniformly adhered on carbon fiber, obtains pretreatment
Carbon fibre fabric.
(2) configuration carbon source and the mixed solution of organo-metallic catalyst presoma
With polythiophene as carbon source, with cobaltous acetate for organo-metallic catalyst presoma, concentration is 0.18g/ml, is carried out by this solution
Ultrasonic 40min, obtains the mixed solution of carbon source and organo-metallic catalyst presoma.
(3) preparation of Folium Pini shape CNT/carbon fibre composite
The carbon fibre fabric of step (1) pretreatment is placed in tube furnace warm area with 120 °, uses chemical vapour deposition technique, argon
The gaseous mixture of 500ml/min and hydrogen 100ml/min is carrier gas, tube furnace with the ramp of 5 DEG C/min to 780 DEG C；Will step
Suddenly the mixed solution that (2) configure is expelled in tube furnace with linear velocity for 0.6ml/min, and keeps reaction furnace pressure constant,
The time of growth CNT is 40min, and growth closes carrier gas after terminating, when temperature reaches 500 DEG C under air atmosphere purification
CNT, treats that tube furnace is down to room temperature and is obtained the Folium Pini shape CNT/carbon fiber composite of preparation on carbon fibre fabric
Material.
The foregoing is only presently preferred embodiments of the present invention, all can prepare Folium Pini shape carbon nanometer according to examples detailed above
Pipe/carbon fibre composite, pattern is as shown in the figure.This technology by change to the temperature of carbon paper heat treatment, the time of acid treatment,
Concentration in carbon source of catalyst iron nitrate concentration, soak time and number of times, metal ion, carrier gas gas speed, growth CNT
The condition such as temperature and time, the Folium Pini shape CNT/stand density of carbon fibre composite, caliber and length can be controlled
Degree.
Claims (10)
1. a preparation method for Folium Pini shape CNT/network combined material with carbon element of electric conduction of carbon fiber, described preparation method be with
The fiber of carbon fibre fabric is growth substrate, the CNT of growing high density arrangement in described growth substrate；Wherein, described
Fibre diameter is 3-10 μm, and the length of described CNT is 5-150 μm, and the diameter of described CNT is 20-220nm, institute
The arranging density stating CNT is 1 × 1021-220×1021Root/m2。
2. preparation method as claimed in claim 1, described preparation method follows these steps to carry out:
(1) the fiber surface pretreatment of carbon fibre fabric
Carbon fibre fabric is placed in ultrasonic cleaning 10-60min in isopropanol or ethanol solution, and dries at a temperature of 60-100 DEG C
Dry 20-60min；After will clean after fabric be placed in tube furnace, control temperature between 500-700 DEG C, at argon atmosphere
Lower calcining 1-12h, carries out high temperature unsticking process to fiber surface；
Carbon fibre fabric high-temperature process crossed is immersed in has in the solution of strong oxidizing property 1-6 hour, takes out and at 60-100
Dry 1-8h at a temperature of DEG C, obtain the carbon fibre fabric of surface cleaning；Inorganic metal catalysis is weighed the most in mass ratio for 25-35:1
Agent presoma and carbohydrate polymer, be dissolved in Ludox and the mixed solvent of surfactant composition that volume ratio is 5-10:1
In, magnetic agitation 6-36h under room temperature, configuration obtains inorganic metal catalyst precursor solution；After by the carbon of above-mentioned surface cleaning
Fabric carries out sucking filtration, 50-100 DEG C of temperature after being placed in inorganic metal catalyst precursor solution immersion 10-120min
Lower drying 3-24h, repeats 1-10 time, makes the carbon fiber surface on fabric wrap up one layer of inorganic metal catalyst presoma equably
With carbohydrate polymer mixture, obtain the carbon fibre fabric of pretreatment；
(2) carbon source is prepared with organo-metallic catalyst precursor mixed solution
Using the material containing aromatic rings class as carbon source, with containing in iron-based, cobalt-based and Ni-based organo-metallic compound
Planting or several as organo-metallic catalyst presoma, organic metal ion concentration in carbon source is 0.01-0.3g/ml；Will
This solution ultrasonic disperse 10-90min, prepares the mixed solution of carbon source and organo-metallic catalyst presoma；
(3) prepared by Folium Pini shape CNT/network combined material with carbon element of electric conduction of carbon fiber
The carbon fibre fabric of step (1) pretreatment is placed in tube furnace warm area with the angle of 0-180 DEG C, uses chemical gaseous phase to sink
Area method, using argon, nitrogen, helium one or more mix as carrier gas for 1-10:1 by volume with hydrogen, tube furnace with
The ramp of 1-10 DEG C/min is to 600-900 DEG C；Mixed solution step (2) configured is with the linear speed of 0.4-2.0ml/min
Degree is injected in tube furnace, keeps reaction furnace pressure constant, and growth time is 15-120min, and growth closes carrier gas after terminating,
When temperature reaches 400-700 DEG C under air atmosphere purifying carbon nano-tube, treat that room temperature is down to by tube furnace, obtain at carbon fibre fabric
The Folium Pini shape CNT of upper preparation/network combined material with carbon element of electric conduction of carbon fiber.
3. preparation method as claimed in claim 1 or 2, described carbon fibre fabric is carbon cloth, carbon fiber tape, carbon fiber
One in paper, carbon fiber felt, carbon fiber seat and carbon fiber plate.
4. preparation method as claimed in claim 1, described strong oxidizing property solvent is in concentrated nitric acid, concentrated sulphuric acid and hydrogen peroxide
Kind, wherein concentrated nitric acid and concentrated sulphuric acid are to be allowed to a kind of or mixing of arbitrary proportion.
5. preparation method as claimed in claim 1, described inorganic metal compound is ferric nitrate, iron chloride, iron phosphate, sulphuric acid
Ferrum, iron sulfide, cobalt nitrate, cobaltous chloride, C.I. Pigment Violet 14, cobaltous sulfate, cobalt sulfide, nickel nitrate, Nickel dichloride., nickel phosphate, nickel sulfate and sulfur
Change the one in nickel or arbitrarily mix.
6. preparation method as claimed in claim 1, described Ludox is neutral Ludox, acidic silicasol and alkaline silica sol
In one, wherein solid silica content is 20%-40%.
7. preparation method as claimed in claim 1, described carbohydrate polymer is glucose, fructose, starch, sucrose, glycogen, wheat
Bud magma essence and cellulose acetate in one or arbitrarily mix.
8. preparation method as claimed in claim 1, described surfactant is ethanol, normal propyl alcohol, isopropanol, dodecyl sulfur
Acid sodium, oleic acid, dodecyl sodium sulfate, dodecylbenzene sodium sulfonate, cetab, lecithin, fatty acid glycerine
One in ester, polyvinyl pyrrolidone, detergent and organic amine soap.
9. preparation method as claimed in claim 2, the material of described aromatic rings class is benzene,toluene,xylene, styrene, benzene
Methanol, benzaldehyde, methyl phenyl ethers anisole, benzene methanamine, benzonitrile, phenylacetic acid, polypyrrole, polythiophene, polyaniline, nitroaniline, double pyridine
One in thioketone and 2-methylimidazole or arbitrarily mix.
10. preparation method as claimed in claim 2, described metallo-organic compound is ferrocene, carbonyl iron, ferric oxalate, vinegar
Acid ferrum, ethylenediamine close ferrum, cobaltocene, carbonyl cobalt, cobalt oxalate, cobaltous acetate, triethylenediamine cobalt, dicyclopentadienyl nickel, Nickel tetracarbonyl., nickel oxalate,
One in nickel acetate and ethylenediamine nickel or arbitrarily mix.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610388144.8A CN106082159B (en) | 2016-06-06 | 2016-06-06 | The preparation method of pine needle shape CNT/network combined carbon material of electric conduction of carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610388144.8A CN106082159B (en) | 2016-06-06 | 2016-06-06 | The preparation method of pine needle shape CNT/network combined carbon material of electric conduction of carbon fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106082159A true CN106082159A (en) | 2016-11-09 |
| CN106082159B CN106082159B (en) | 2017-12-08 |
Family
ID=57447450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610388144.8A Active CN106082159B (en) | 2016-06-06 | 2016-06-06 | The preparation method of pine needle shape CNT/network combined carbon material of electric conduction of carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106082159B (en) |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711427A (en) * | 2017-02-22 | 2017-05-24 | 清华大学深圳研究生院 | Anode material for lithium sulfur battery and using method thereof |
| CN106971859A (en) * | 2017-04-14 | 2017-07-21 | 同济大学 | A kind of carbon fiber/carbon nanotube flexible super capacitor electrode material and its preparation |
| CN108336292A (en) * | 2017-01-19 | 2018-07-27 | 中国石油化工股份有限公司 | A kind of electrode and preparation method thereof and a kind of carbon nanotube and its application |
| CN108630926A (en) * | 2018-05-07 | 2018-10-09 | 中国科学院成都有机化学有限公司 | A kind of lithium-sulphur cell positive electrode and preparation method thereof containing short carbon fiber silk |
| CN109610159A (en) * | 2018-12-20 | 2019-04-12 | 山东大学 | A kind of preparation method growing carbon nanotube in carbon fibre fabric surface catalysis using bimetallic catalyst |
| CN109750492A (en) * | 2018-12-20 | 2019-05-14 | 山东大学 | A kind of surface treatment method of carbon cloth surfaces homoepitaxial carbon nanotube early period |
| CN110342492A (en) * | 2019-06-13 | 2019-10-18 | 兰溪市立顺生物有限公司 | A kind of preparation method of nitrating oxygen carbon nanotube/porous charcoal |
| CN110403589A (en) * | 2018-04-28 | 2019-11-05 | 五邑大学 | A kind of disposable heart rate patch |
| CN110479310A (en) * | 2019-09-04 | 2019-11-22 | 西南石油大学 | The preparation and application of supported sulfided Co catalysts for selectivity synthesis carbon nanotube |
| CN110844899A (en) * | 2019-10-28 | 2020-02-28 | 广州大学 | Carbon nano tube composite cobalt sulfide nano material and preparation method and application thereof |
| CN110890552A (en) * | 2018-09-07 | 2020-03-17 | 赛高创新株式会社 | Method for producing battery electrode, and battery electrode |
| CN110886089A (en) * | 2019-11-19 | 2020-03-17 | 杭州超探新材料有限公司 | Preparation method of graphene and carbon nanotube in-situ growth co-modified toughened carbon fiber |
| CN112421055A (en) * | 2020-10-27 | 2021-02-26 | 太原理工大学 | Preparation method and application of oxidized nitrogen-doped carbon nanotube array cluster/flexible carbon fiber material integrated electrode |
| CN112751015A (en) * | 2019-10-31 | 2021-05-04 | 青岛海尔智能技术研发有限公司 | Zinc cathode and preparation method thereof, zinc-air battery and direct current water heater |
| CN109265191B (en) * | 2018-08-13 | 2021-06-22 | 南京滕峰科技有限公司 | Preparation method and application of nano onion carbon/carbon fiber composite electrode material |
| CN113044839A (en) * | 2021-04-02 | 2021-06-29 | 清创人和生态工程技术有限公司 | Preparation method and application of hierarchical porous carbon material |
| CN113490639A (en) * | 2018-08-21 | 2021-10-08 | 纳瓦科技公司 | Method for growing carbon nanotubes on the surface and in the bulk of a porous carbonaceous substrate and use for preparing an electrode |
| CN113593926A (en) * | 2021-07-19 | 2021-11-02 | 常州大学 | Preparation method of conductive polymer modified carbon nanotube-based flexible self-supporting energy storage device electrode material |
| CN115072696A (en) * | 2022-04-29 | 2022-09-20 | 西安交通大学苏州研究院 | Co-NCNT @ HC hierarchical porous carbon material and preparation method and application thereof |
| CN115262278A (en) * | 2022-08-01 | 2022-11-01 | 浙江科技学院 | Preparation method of high-uniformity double-layer gradient hole carbon paper base paper |
| CN115340131A (en) * | 2022-08-31 | 2022-11-15 | 盐城工学院 | Preparation method of cobalt disulfide-polythiophene wave-absorbing material |
| CN115538147A (en) * | 2022-09-26 | 2022-12-30 | 贵州梅岭电源有限公司 | Preparation method of three-dimensional fluorinated carbon fiber flexible electrode |
| CN115678304A (en) * | 2022-12-29 | 2023-02-03 | 北京碳垣新材料科技有限公司 | Carbon nano tube composite material, preparation method and preparation device |
| CN116497596A (en) * | 2023-03-15 | 2023-07-28 | 大连工业大学 | Single-walled carbon nanotube/flexible fabric composite electrothermal film and preparation method and application thereof |
| CN116789108A (en) * | 2023-07-19 | 2023-09-22 | 烯格沃(上海)纳米技术有限公司 | Composition and method for improving yield of single-walled carbon nanotubes |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351166A (en) * | 2011-06-30 | 2012-02-15 | 中国科学院上海硅酸盐研究所 | Method for directly growing carbon nanotube on surface of carbon fiber |
| CN102354612A (en) * | 2011-09-06 | 2012-02-15 | 天津大学 | Array carbon nano-tube/carbon fiber-based flexible composite electrode material and preparation method thereof |
| CN103337639A (en) * | 2013-06-24 | 2013-10-02 | 太原理工大学 | Preparation method of carbon nano tube array/carbon fiber fabric integrated three-dimensional porous air electrode |
| CN105272326A (en) * | 2015-11-23 | 2016-01-27 | 哈尔滨工业大学 | Preparation method and application of carbon nano tube modified carbon fiber enhanced SiBCN ceramic composite material |
-
2016
- 2016-06-06 CN CN201610388144.8A patent/CN106082159B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351166A (en) * | 2011-06-30 | 2012-02-15 | 中国科学院上海硅酸盐研究所 | Method for directly growing carbon nanotube on surface of carbon fiber |
| CN102354612A (en) * | 2011-09-06 | 2012-02-15 | 天津大学 | Array carbon nano-tube/carbon fiber-based flexible composite electrode material and preparation method thereof |
| CN103337639A (en) * | 2013-06-24 | 2013-10-02 | 太原理工大学 | Preparation method of carbon nano tube array/carbon fiber fabric integrated three-dimensional porous air electrode |
| CN105272326A (en) * | 2015-11-23 | 2016-01-27 | 哈尔滨工业大学 | Preparation method and application of carbon nano tube modified carbon fiber enhanced SiBCN ceramic composite material |
Non-Patent Citations (2)
| Title |
|---|
| YU LI ET AL: "Preparation and structural evolution of well aligned-carbon nanotube arrays onto conductive carbon-black layer/carbon paper substrate with enhanced discharge capacity for Li–air batteries", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 黄彦芳等: "导电活性碳层/碳纸基底上碳纳米管阵列的可控制备", 《太原理工大学学报》 * |
Cited By (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108336292A (en) * | 2017-01-19 | 2018-07-27 | 中国石油化工股份有限公司 | A kind of electrode and preparation method thereof and a kind of carbon nanotube and its application |
| CN112086643A (en) * | 2017-01-19 | 2020-12-15 | 中国石油化工股份有限公司 | Carbon nano tube and application thereof |
| CN106711427B (en) * | 2017-02-22 | 2019-07-02 | 清华大学深圳研究生院 | A kind of positive material for lithium-sulfur battery and its application method |
| CN106711427A (en) * | 2017-02-22 | 2017-05-24 | 清华大学深圳研究生院 | Anode material for lithium sulfur battery and using method thereof |
| CN106971859A (en) * | 2017-04-14 | 2017-07-21 | 同济大学 | A kind of carbon fiber/carbon nanotube flexible super capacitor electrode material and its preparation |
| CN110403589A (en) * | 2018-04-28 | 2019-11-05 | 五邑大学 | A kind of disposable heart rate patch |
| CN108630926A (en) * | 2018-05-07 | 2018-10-09 | 中国科学院成都有机化学有限公司 | A kind of lithium-sulphur cell positive electrode and preparation method thereof containing short carbon fiber silk |
| CN108630926B (en) * | 2018-05-07 | 2021-09-03 | 中国科学院成都有机化学有限公司 | Lithium-sulfur battery positive electrode containing short carbon fiber filaments and preparation method thereof |
| CN109265191B (en) * | 2018-08-13 | 2021-06-22 | 南京滕峰科技有限公司 | Preparation method and application of nano onion carbon/carbon fiber composite electrode material |
| CN113490639A (en) * | 2018-08-21 | 2021-10-08 | 纳瓦科技公司 | Method for growing carbon nanotubes on the surface and in the bulk of a porous carbonaceous substrate and use for preparing an electrode |
| CN110890552A (en) * | 2018-09-07 | 2020-03-17 | 赛高创新株式会社 | Method for producing battery electrode, and battery electrode |
| CN109610159A (en) * | 2018-12-20 | 2019-04-12 | 山东大学 | A kind of preparation method growing carbon nanotube in carbon fibre fabric surface catalysis using bimetallic catalyst |
| CN109610159B (en) * | 2018-12-20 | 2020-03-20 | 山东大学 | Preparation method for catalytic growth of carbon nanotubes on surface of carbon fiber fabric by using bimetallic catalyst |
| CN109750492A (en) * | 2018-12-20 | 2019-05-14 | 山东大学 | A kind of surface treatment method of carbon cloth surfaces homoepitaxial carbon nanotube early period |
| CN110342492A (en) * | 2019-06-13 | 2019-10-18 | 兰溪市立顺生物有限公司 | A kind of preparation method of nitrating oxygen carbon nanotube/porous charcoal |
| CN110342492B (en) * | 2019-06-13 | 2021-03-09 | 陕西浦士达环保科技有限公司 | Preparation method of nitrogen-oxygen doped carbon nano tube/porous carbon |
| CN110479310B (en) * | 2019-09-04 | 2022-03-25 | 西南石油大学 | Preparation and application of supported cobalt sulfide catalyst for selectively synthesizing carbon nano tube |
| CN110479310A (en) * | 2019-09-04 | 2019-11-22 | 西南石油大学 | The preparation and application of supported sulfided Co catalysts for selectivity synthesis carbon nanotube |
| CN110844899A (en) * | 2019-10-28 | 2020-02-28 | 广州大学 | Carbon nano tube composite cobalt sulfide nano material and preparation method and application thereof |
| CN112751015A (en) * | 2019-10-31 | 2021-05-04 | 青岛海尔智能技术研发有限公司 | Zinc cathode and preparation method thereof, zinc-air battery and direct current water heater |
| CN112751015B (en) * | 2019-10-31 | 2022-07-26 | 青岛海尔智能技术研发有限公司 | Zinc cathode and preparation method thereof, zinc-air battery and direct current water heater |
| CN110886089B (en) * | 2019-11-19 | 2022-01-07 | 杭州超探新材料科技有限公司 | Preparation method of graphene and carbon nanotube in-situ growth co-modified toughened carbon fiber |
| CN110886089A (en) * | 2019-11-19 | 2020-03-17 | 杭州超探新材料有限公司 | Preparation method of graphene and carbon nanotube in-situ growth co-modified toughened carbon fiber |
| CN112421055A (en) * | 2020-10-27 | 2021-02-26 | 太原理工大学 | Preparation method and application of oxidized nitrogen-doped carbon nanotube array cluster/flexible carbon fiber material integrated electrode |
| CN112421055B (en) * | 2020-10-27 | 2022-02-22 | 太原理工大学 | Preparation method and application of oxidized nitrogen-doped carbon nanotube array cluster/flexible carbon fiber material integrated electrode |
| CN113044839B (en) * | 2021-04-02 | 2022-09-16 | 清创人和生态工程技术有限公司 | Preparation method and application of hierarchical porous carbon material |
| CN113044839A (en) * | 2021-04-02 | 2021-06-29 | 清创人和生态工程技术有限公司 | Preparation method and application of hierarchical porous carbon material |
| CN113593926B (en) * | 2021-07-19 | 2023-01-17 | 常州大学 | Preparation method of conductive polymer modified carbon nanotube-based flexible self-supporting energy storage device electrode material |
| CN113593926A (en) * | 2021-07-19 | 2021-11-02 | 常州大学 | Preparation method of conductive polymer modified carbon nanotube-based flexible self-supporting energy storage device electrode material |
| CN115072696A (en) * | 2022-04-29 | 2022-09-20 | 西安交通大学苏州研究院 | Co-NCNT @ HC hierarchical porous carbon material and preparation method and application thereof |
| CN115262278A (en) * | 2022-08-01 | 2022-11-01 | 浙江科技学院 | Preparation method of high-uniformity double-layer gradient hole carbon paper base paper |
| CN115262278B (en) * | 2022-08-01 | 2023-06-16 | 浙江科技学院 | Preparation method of high-uniformity double-layer gradient pore carbon paper base paper |
| WO2024026908A1 (en) * | 2022-08-01 | 2024-02-08 | 浙江科技学院 | Method for preparing high-uniformity double-layer raw carbon paper having gradient pore size |
| CN115340131A (en) * | 2022-08-31 | 2022-11-15 | 盐城工学院 | Preparation method of cobalt disulfide-polythiophene wave-absorbing material |
| CN115340131B (en) * | 2022-08-31 | 2023-06-02 | 盐城工学院 | Preparation method of cobalt disulfide-polythiophene wave-absorbing material |
| CN115538147A (en) * | 2022-09-26 | 2022-12-30 | 贵州梅岭电源有限公司 | Preparation method of three-dimensional fluorinated carbon fiber flexible electrode |
| CN115538147B (en) * | 2022-09-26 | 2023-10-17 | 贵州梅岭电源有限公司 | Preparation method of three-dimensional carbon fluoride fiber flexible electrode |
| CN115678304A (en) * | 2022-12-29 | 2023-02-03 | 北京碳垣新材料科技有限公司 | Carbon nano tube composite material, preparation method and preparation device |
| CN116497596A (en) * | 2023-03-15 | 2023-07-28 | 大连工业大学 | Single-walled carbon nanotube/flexible fabric composite electrothermal film and preparation method and application thereof |
| CN116789108A (en) * | 2023-07-19 | 2023-09-22 | 烯格沃(上海)纳米技术有限公司 | Composition and method for improving yield of single-walled carbon nanotubes |
| CN116789108B (en) * | 2023-07-19 | 2024-05-17 | 烯格沃(上海)纳米技术有限公司 | Composition and method for improving yield of single-walled carbon nanotubes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106082159B (en) | 2017-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106082159A (en) | The preparation method of Folium Pini shape CNT/network combined material with carbon element of electric conduction of carbon fiber | |
| Jiang et al. | Recent advances in carbon-based electrocatalysts for vanadium redox flow battery: Mechanisms, properties, and perspectives | |
| CN107235472B (en) | Porous vertical graphene nano wall array of N doping and the preparation method and application thereof | |
| Fan et al. | Carbon nanosheets: synthesis and application | |
| CN109671576A (en) | Carbon nano tube-MXene composite three-dimensional porous carbon material and preparation method thereof | |
| CN109192985B (en) | ZIF-9-based porous carbon/carbon fiber composite material and preparation method thereof | |
| CN105597791B (en) | A kind of selenizing molybdenum/porous carbon nanofiber composite material and preparation method and application | |
| CN105271217B (en) | A kind of preparation method of the three-dimensional grapheme of N doping | |
| CN106229521B (en) | A kind of FeCx@NC catalyst with core-casing structure and preparation method thereof | |
| US20150352522A1 (en) | Carbon material for catalyst support use | |
| CN104973596B (en) | A kind of Heteroatom doping hollow ball graphene composite material and preparation method and application | |
| CN102354612B (en) | Array carbon nano-tube/carbon fiber-based flexible composite electrode material and preparation method thereof | |
| CN102683044A (en) | Combined electrode for super capacitor and preparation method thereof | |
| CN104045077A (en) | Graphene three-dimensional hierarchical porous carbon material and preparation method thereof | |
| WO2021036219A1 (en) | Molybdenum disulfide/graphene/carbon composite material and use thereof | |
| CN106025242B (en) | Lithium ion battery silicon alloy nano wire composite negative pole material and preparation method thereof | |
| CN107715899A (en) | A kind of nanometer phosphatization cobalt porous carbon nanofiber flexible membrane and preparation method thereof | |
| CN106048650A (en) | 3D porous electrode preparation method and use of 3D porous electrode in electrochemical hydrogen evolution | |
| CN109243862B (en) | Dual-modified carbon hollow sphere compound and preparation method and application thereof | |
| Liu et al. | Carbon nanomaterials with hollow structures: a mini-review | |
| CN107680821A (en) | A kind of double-metal hydroxide@nickel molybdate@graphene nanocomposite materials, preparation method and applications | |
| CN107196020A (en) | The preparation method of nitrogen-doped carbon nanometer pipe array/carbon fibre material air electrode | |
| CN106653384B (en) | Functional amido graphene quantum dot/carbon nanotube/carbon cloth three-dimension flexible electrode preparation method | |
| CN110148760A (en) | A kind of porous carbon-carbon nano tube compound material and its preparation method and application | |
| CN105789645A (en) | Pt/WO3-RGO catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 030600, 209, University street, Yuci District, Shanxi, Jinzhong Patentee after: Taiyuan University of Technology Address before: 030024 Yingze, Shanxi Province, Berlin District, West Street, No. 79, No. Patentee before: Taiyuan University of Technology |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190416 Address after: 030027 Shanxi Taiyuan Comprehensive Reform Demonstration Zone Taiyuan Tanghuai Park, 49 Zhengyang Street, 6th floor Jinchuang Company A005 Patentee after: Qingchuang Man and Ecological Engineering Technology Co., Ltd. Address before: 030600 University Street 209, Yuci District, Jinzhong City, Shanxi Province Patentee before: Taiyuan University of Technology |